Reaction of [Pd2Cl2(dppm)2] 1 with arenesulfonyl azides RSO2N, in CH2Cl2 at ambient temperature resulted in the formation of dimeric palladium complexes with bridging arylsulfonylnitrene ligands [Pd2Cl2(dppm)2(μ-NSO2R)] 2(R = phenyl a, 4-methylphenyl b, 4-nitrophenyl c, 2-nitrophenyl d, 2-naphthyl e or ferrocenyl f). According to their NMR spectra, complexes 2a-2f are typical A-frame adducts, which has been verified by single crystal X-ray diffraction studies on 2d-2f. The short N(1)-S(1) distances [1.541(3)-1.565(3) Å] reflect the double bond character of these bonds and indicate a dπ-pπ interaction of the sulfur atom and the imido nitrogen atom. With 2-nitrobenzene-sulfonyl azide a by-product was observed in a yield of 10-15%. Based on spectroscopic properties (1H and 31P NMR, IR) and elemental analysis, this compound contains a bridging arenesulfonyl azide ligand, [Pd2Cl2(dppm)2(μ-2-O2NC 6-H4SO2N3)] 3d. Irradiation with light of λ > 455 nm caused selective dissociation of 3d into 1 and 2-O2NC6H4SO2N3. The azide complex 3d is not an intermediate in the formation of the corresponding nitrene complex 2d.
|Number of pages||7|
|Journal||Journal of the Chemical Society - Dalton Transactions|
|Publication status||Published - Feb 7 1999|
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